EP3388392B1 - Kupfer enthaltende, kleinporige zeolite mit niedrigerm alkalimetallgehalt, verfahren zu ihrer herstellung und ihre verwendung als scr-katalysatoren - Google Patents

Kupfer enthaltende, kleinporige zeolite mit niedrigerm alkalimetallgehalt, verfahren zu ihrer herstellung und ihre verwendung als scr-katalysatoren Download PDF

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EP3388392B1
EP3388392B1 EP17166394.1A EP17166394A EP3388392B1 EP 3388392 B1 EP3388392 B1 EP 3388392B1 EP 17166394 A EP17166394 A EP 17166394A EP 3388392 B1 EP3388392 B1 EP 3388392B1
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Prior art keywords
zeolite
copper
pore
containing small
tepa
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French (fr)
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EP3388392A1 (de
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Frank-Walter Schuetze
Leen VAN TENDELOO
Stephan Eckhoff
Dirk Van Genechten
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Umicore AG and Co KG
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Umicore AG and Co KG
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Priority to EP17166394.1A priority Critical patent/EP3388392B1/de
Priority to EP18717894.2A priority patent/EP3609838A1/de
Priority to CN201880024780.XA priority patent/CN110546108B/zh
Priority to PCT/EP2018/059156 priority patent/WO2018189177A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to copper-containing small-pore zeolites for use in the selective catalytic reduction of nitrogen oxides by reaction with NH 3 as reductant (NH 3 -SCR), a one-step synthesis method of preparing these copper-containing small-pore zeolites according to the invention as well as towards the use in NH3-SCR catalysis.
  • the invention provides a copper-containing CHA-type catalyst, wherein the zeolite contains 2 to 7 wt.-% copper oxide, 0.1 to 0.4 wt.-% alkali cations, and has a BET surface area of 320 to 750 m 2 /g.
  • Zeolites are microporous aluminosilicate materials which have very regular pore structures of molecular dimensions and which occur in numerous framework structures. They are classified by the Structure Commission of the International Zeolite Association which defines respective framework types. The commission also assigns framework type codes consisting of three capital letters to all unique and confirmed framework topologies. For example, a widely used group of zeolites belongs to the faujasite framework to which the code FAU has been assigned.
  • zeolites with a large pore size have a maximum ring size of 12 tetrahedral atoms
  • zeolites with a medium pore size have a maximum pore size of 10
  • zeolites with a small pore size have a maximum pore size of 8 tetrahedral atoms.
  • Well-known small-pore zeolites belong in particular to the AEI, CHA (chabazite), ERI (erionite), LEV (levyne) and KFI framework types. Examples having a large pore size are zeolites of the faujasite framework type.
  • Small-pore zeolites in particular if cations like copper and iron are included in the zeolite pores, play an important role as catalysts in the so-called Selective Catalytic Reduction (SCR) of nitrogen oxides with ammonia to form nitrogen and water.
  • SCR Selective Catalytic Reduction
  • the SCR process has been widely used to clean up exhaust gases which result from the combustion of fossil fuels, in particular from stationary power plants and from vehicles powered by diesel engines.
  • Nitric oxide (NO) is the main NO x compound produced in an engine.
  • the reduction of NO is referred to as the "standard" NH 3 -SCR reaction: 4NO + 4NH 3 + O 2 ⁇ 4N 2 + 6H 2 0 (1)
  • NO 2 is more reactive than NO.
  • the NH 3 -SCR reaction is easier, and the so-called “fast” NH 3 -SCR reaction can occur: 2NH 3 + NO + NO 2 ⁇ 2N 2 + 3H 2 O (2)
  • hydrothermal stability of SCR catalysts is another essential parameter, as an NH 3 -SCR catalyst has to withstand harsh temperature conditions under full load of the engine and the exposure to water vapor at temperatures up to 700 °C is known to be critical for many zeolite types.
  • zeolites occur in nature, zeolites intended for use as SCR catalyst or other industrial applications are usually manufactured via synthetic processes.
  • WO 2011/073398 A2 discloses processes for the preparation of copper-containing molecular sieves with the CHA structure, wherein the copper is exchanged into the Na + form of the Chabazite, using a liquid copper solution wherein the concentration of copper is in the range of about 0.001 to about 0.4 molar. Also described are copper-containing molecular sieves with the CHA structure, catalysts incorporating molecular sieves, systems and methods for their use.
  • the CHA zeolite contains 2 to 5 wt.-%, 2 to 4 wt.-%, 2.5 to 3.5 wt.-%, and 2.75 to 3.75 wt.-% of copper, calculated as CuO; containing sodium metal cations in a total amount of 0.1, 0.2 and 0.25 wt.-%; and having a BET surface area of from 600 to 750 m 2 /g.
  • the SAR values is between 15 and 20; the copper to aluminum atomic ratio is in the ranges of between 0.25 to 0.5 and 0.3 to 0.4; and the crystallite size ranges from 50 to 500 nm.
  • WO 2011/073390 A2 discloses processes for the preparation of copper-containing molecular sieves with the CHA structure having a silica to alumina mole ratio greater than about 10, wherein the copper exchange step is conducted via wet state exchanged and prior to the coating step, and wherein in the copper exchange step a liquid copper solution is used wherein the concentration of copper is in the range of about 0.001 to about 0.25 molar using copper acetate and/or an ammoniacal solution of copper ions as copper source.
  • Catalysts made by the processes, catalyst systems and methods of treating exhaust gas with the molecular sieves and catalysts are also disclosed.
  • the molecular sieve with the CHA structure has a copper content, calculated as CuO, ranging from about 2 to about 5 wt.-%.
  • the silica to alumina ratio is preferably greater than about 15, more specifically in the range from about 25 to about 40.
  • the sodium content is below 2 wt.-%, specifically below 1 wt.-%,even more specifically below 2000 ppm, 1000 ppm, 500 ppm, and most specifically below 100 ppm.
  • the copper-containing molecular sieve with the CHA structure exhibits a BET surface area in the range from about 400 to about 750 m 2 /g.
  • US 4,544,538 describes the hydrothermal synthesis of small-pore zeolite SSZ-13 with CHA framework type using a source of aluminum and silicon, an alkali hydroxide and an organic structure directing agent, for example N,N,N-trimethyl-1-adamantammonium iodide, N-methyl-3-quinuclidinol iodide or N,N,N-trimethyl-2-ammonium exonorborane.
  • Copper introduction needs to be performed by an additional unit operation such as ion exchange, impregnation and the like.
  • a disadvantage of this approach is the need of expensive templates and an additional processing step for the copper loading.
  • WO2009/141324 discloses a process for the preparation of a copper containing zeolitic material having CHA framework structure which comprises using a source of aluminum, a source of silicon and a source of copper. Also this process needs a structure directing agent as a template for the CHA framework structure, for example 1- adamantyltrimethylammonium hydroxide and benzyltrimethylammonium hydroxide.
  • This one-pot process for the manufacture of copper containing aluminosilicate zeolites has disadvantages. For example, it involves organic templates as structure directing agents which are usually very expensive.
  • a one-pot synthesis of copper containing CHA zeolite is also described in WO 2015/084817 A1 , WO 2015/084930 A1 and US 2015/0151286 A1 .
  • a mixed-template approach is combined with a silica source, alumina source and optional seed crystals of the envisaged zeolite framework.
  • the mixed-template comprises a metal-amine complex, preferably copper tetraethylenepentamine (Cu-TEPA), and a second organic structure direct agent suitable for forming the envisaged zeolite framework, such as N,N,Ndimethylethylcyclohexylammonium, N,N,N- methyldiethylcyclohexyl-ammonium, N,N,N-triethylcyclohexylammonium, benzyltrimethyl-ammonium, tetramethylammonium, 1 -adamantyltrimethlylammonium and N,N,N-triethylcyclohexylammonium cations, in the case CHA zeolite framework is preferred.
  • a metal-amine complex preferably copper tetraethylenepentamine (Cu-TEPA)
  • Cu-TEPA copper tetraethylenepentamine
  • the final gel had the following molar ratios: 1 SiO 2 / 0.047 Al 2 O 3 / 0.05 Cu-TEPA / 0.4 TEAOH /0.1 NaOH /5H 2 O. Similar, the disadvantage is the use of organic templates which are usually very expensive.
  • the resulting material has a Si/AI ratio of 4.15 and a CuO and Na 2 O content of 12.89 wt.% and 12.41 wt.%, respectively.
  • Ion exchange of the as made zeolite with 1 M NH 4 NO 3 decreases the CuO and Na 2 O content to 3.8 and 1.2 wt.%, respectively.
  • US 2011/0165051 A1 discloses processes for the preparation of copper containing molecular sieves with the CHA structure wherein the copper is exchanged into the Na + -form of the Chabazite, using a liquid copper solution wherein the concentration of copper is in the range of about 0.0001 to about 0.4 molar.
  • the method for preparing the molecular sieves with the CHA structure uses adamantyltrimethylammonium hydroxide as the structure directing agent.
  • the process includes a copper exchange step wherein a zeolite is dispersed in a copper solution.
  • the method provided does not allow for an independent adjustment of the copper and the sodium contents, respectively, because sodium cations replace copper cations.
  • the embodiments presented can be modified so that the sodium content is less than about 2500 ppm, corresponding to 0.25 wt.-%. However, sodium contents range from 0.25 to 2 wt.-%.
  • the molecular sieve with the CAH structure may be provided in the form of a powder or a sprayed material. Subsequently, the powder or sprayed material is admixed with or coated by suitable modifiers such as silica, alumina, zeolites or refractory binders.
  • suitable modifiers such as silica, alumina, zeolites or refractory binders.
  • the copper is exchanged into the Na + -form of the Chabazite, using a liquid copper solution, but in US 2011/0165052 A1 , the concentration of copper is in the range of about 0.0001 to about 0.25 molar.
  • the processes for the manufacture of copper containing aluminosilicate zeolites described above have disadvantages. For example, they involve several process steps including crystallization of the final product at about 150 °C and high pressure which results in a high energy consumption and an ion exchange step to remove the excessive copper content. They do not allow for adjusting the copper and sodium or alkali metal independently from one another. Furthermore, the selectivity, activity and hydrothermal stability of many Cu-containing small-pore zeolites known so far is not sufficient for long-term applications in automotive combustion exhaust purification systems.
  • the inventors of the present invention have now surprisingly found crystalline copper-containing small-pore aluminosilicate zeolites having a maximum pore size of eight tetrahedral atoms, wherein the zeolite is CHA, containing 2 to 7 wt.-% copper, calculated as CuO and based on the total weight of the respective zeolite, and containing alkali metal cations in a total amount of 0.1 to 0.4 wt.-%, calculated as pure metals and based on the total weight of the zeolite, wherein the alkali metals are selected from sodium, potassium and mixtures of sodium and potassium, and having a SAR of 7 to 9, and having a BET surface area of from 600 to 750 m 2 /g.
  • novel copper-containing zeolites according to the present invention the process for making them and the method for using them as SCR catalysts are explained below, with the invention encompassing all the embodiments indicated below, both individually and in combination with one another.
  • a crystal structure is a description of the ordered arrangement of atoms, ions, or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric patterns that repeat along the principal directions of three-dimensional space in matter.
  • a “crystal” therefore represents a solid material whose constituents are arranged in a crystal structure.
  • a “crystalline substance” is composed of crystals.
  • a "zeolite framework type”, also referred to as “framework type”, represents the corner-sharing network of tetrahedrally coordinated atoms. For instance, a "CHA framework type material” is a zeolitic material having a CHA framework type.
  • the crystalline copper-containing small-pore aluminosilicate zeolites according to the present invention having a maximum pore size of eight tetrahedral atoms, wherein the zeolite is CHA, containing 2 to 7 wt.-% copper, calculated as CuO and based on the total weight of the respective zeolite, and containing alkali metal cations in a total amount of 0.1 to 0.4 wt.-%, calculated as pure metals and based on the total weight of the zeolite, wherein the alkali metals are selected from sodium, potassium and mixtures of sodium and potassium, and having a SAR of 7 to 9, and having a BET surface area of from 600to 750 m 2 /g are hereinafter referred to as "the zeolites" or "the zeolites according to the present invention".
  • the silica to alumina ratio ranges from 7 to 9.
  • the silica to alumina molar ratio is abbreviated as SAR.
  • the zeolites according to the present invention comprise copper in an amount of 2 to 7 wt.-%, preferably 3 to 6 wt.-%, even more preferably 3 to 5 wt.-%, calculated as CuO and based on the total weight of the respective zeolite.
  • the copper to aluminum atomic ratio of the zeolites is in the range of between 0.003 to 0.6, preferably 0.05 to 0.5, particularly preferably 0.1 to 0.5.
  • the zeolites according to the present invention contain alkali metal cations in a total amount of 0.1 to 0.4 wt.-%, calculated as pure metals and based on the total weight of the zeolite.
  • the zeolite is CHA and the alkali metal is sodium, potassium, or a mixture of sodium and potassium.
  • the crystallite size of the zeolites according to the invention measured by SEM is between 10 nm to 5000 nm, preferably 20 nm to 2000 nm, even more preferably between 50 nm and 1000 nm, and most preferably between 50 nm and 500 nm.
  • the BET surface area can be measured according to ISO 9277.
  • the zeolite is CHA, and its BET surface area is between 600 and 750 m 2 /g.
  • the zeolite is CHA, has a copper content of from 2 to 7 wt.-%, calculated as CuO and based on the total weight of the zeolite, and a content of alkali metal cations in a total amount of 0.1 to 0.4 wt.-%, calculated as pure metals and based on the total weight of the zeolite, wherein the alkali metals are selected from sodium, potassium and mixtures of sodium and potassium, a SAR of 7 to 9, and a BET surface area of from 600 to 750 m 2 /g.
  • the copper-containing small-pore zeolites according to the present invention can be used for the preparation of SCR catalysts. Furthermore, they are suitable ion exchangers. They can also be used as molecular sieves and as catalysts in a large variety of reactions. Well-known uses of zeolites include, for instance, fluid catalytic cracking, hydrocracking, hydrocarbon conversion reactions, reprocessing methods and heat accumulation.
  • the object to provide a simple, cost-effective process for making the crystalline, copper-containing small-pore aluminosilicate zeolites according to the present invention is solved as described hereinafter.
  • This method and its embodiments are easy to perform while having a reduced energy consumption, yielding the zeolites according to the present invention as described above with the desired CuO content between 2 and 7 wt.-%, the content of alkali metal cations of 0.1 to 0.4 wt.-% and the BET surface area of between 600 and 750 m 2 /g and go without use of expensive templates.
  • the inventors of the present invention have now found that it is surprisingly possible to transform zeolites of the faujasite framework type under alkaline conditions in the presence of a copper complex with tetraethylenepentamine (TEPA) to copper containing small-pore zeolites.
  • TEPA tetraethylenepentamine
  • reaction mixture refers to an aqueous mixture.
  • the reaction mixture does not comprise the tetraethylammonium, tetramethylammonium, N,N,N-dimethylethyl-cyclohexylammonium, N,N,N- methyldiethylcyclohexyl-ammonium, N,N,N-triethylcyclohexylammonium, benzyltrimethyl-ammonium, 1-adamantyl-trimethlylammonium, N,N,N-triethylcyclo-hexylammonium and the N,N-dimethyl-3,5-dimethylpiperidinium cations.
  • the heating is performed at temperatures of 80 to 150 °C, in particular 90 to 98 °C, for 2 to 31 days.
  • the reaction mixture is left statical, i.e. it stands without stirring, during the heating step.
  • the copper containing small-pore zeolite is calcined, and the copper and alkali metal content of the copper containing small-pore aluminosilicate zeolites is further adjusted via ion exchange techniques. Such techniques are well known to the skilled artisan.
  • an ammonium exchange is performed in order to remove part of the alkali metal or copper cations from the zeolite framework by replacing them with NH 4 + cations.
  • the copper and alkali metal content of the resulting crystalline copper-containing small-pore aluminosilicate zeolites can be easily controlled via the amount of ammonium cations and the number of ion exchange procedures performed.
  • an NH 4 + liquid ion exchange can be performed at 100 °C in an aqueous suspension under reflux conditions. 100 ml of a 0.5 M aqueous NH 4 Cl or NH 4 NO 3 solution is used per 1 g of the zeolite.
  • the calcining step is carried out for 1 to 5 hours at temperatures of between 500°C and 650°C. Preferable, the calcination is carried out for 2 hours at about 600°C.
  • ammonium cations decompose upon heating: ammonia (NH 3 ) escapes, and a proton (H + ) remains at the site where NH 4 + has formerly been. If the copper containing zeolite is first ion exchanged and then calcined, metal cations (copper and/or alkali cations) will first be replaced by NH 4 + and then by H + due to the thermal decomposition of NH 4 + .
  • the copper containing small-pore zeolites may be used in SCR catalysis. If the copper containing zeolite is first calcined and then ion exchanged according to the processed described above, NH 4 + cations will decompose in the same manner as described above for the calcination, but during hydrothermal aging of the SCR catalyst.
  • ammonium ion exchange eventually results in a replacement of some of the copper and/or alkali metal cations by protons, irrespective of whether the ion exchange is carried out first, followed by calcination or vice versa.
  • tetraethylenepentamine is the only structure directing agent in the reaction mixture.
  • structure directing agents also called “structure directing templates” are organic molecules comprising relatively hydrophobic, bulky and rigid organic cations. Said SDAs determine the structure of the respective zeolite which is formed during SiO 2 crystallization.
  • Zeolites of the faujasite framework type are known and commercially available in a large variety under the name zeolite Y.
  • zeolite Y a large amount of faujasites with different Si/AI ratios is available which allows easy control of the Si/AI ratio of the resulting copper containing small-pore zeolite.
  • the zeolite of the faujasite framework type has a Si/AI ratio in the range from 5 to 30.
  • the copper content of the resulting copper containing small-pore zeolite can be easily controlled via the amount of copper complex used in the inventive process.
  • the copper content of the copper containing small-pore zeolite is 2 to 7 wt.-%, in particular 3 to 6 wt.-% and particularly preferably 3 to 5 wt.%, calculated as CuO and based on the total weight of the copper containing small-pore zeolite.
  • the copper complexing agent TEPA used in the inventive process is known and commercially available.
  • the Cu-TEPA can be manufactured in line with known processes, see for example the procedure described under "Embodiments" below.
  • the copper complex is used in an amount of 0.0001 mole/wt Cu-TEPA/FAU zeolite to 0.0016 mole/wt Cu-TEPA/FAU zeolite.
  • the compound M(OH) x is NaOH and/or KOH and the copper containing small-pore zeolite obtained is of the CHA framework type.
  • M(OH) x is used in an amount of 0.001 mole/wt M(OH) x /FAU zeolite to 0.025 mole/wt M(OH) x /FAU zeolite.
  • Exhaust emissions of vehicles driven by a predominantly lean combustion engine contain, next to particle emission, in particular the primary emissions carbon monoxide CO, hydrocarbons HC, and nitrogen oxides NO x . Due to the relatively high oxygen content of up to 15 vol.%, carbon monoxide and hydrocarbons can be rendered harmless by oxidation fairly easy, but the reduction of the nitrogen oxides to nitrogen is much more difficult to achieve.
  • An SCR catalyst containing a zeolite according to the present invention may be manufactured by well-known methods.
  • the SCR catalysts may, for instance, be obtained by solid state sublimation.
  • a dry, intimate mixture of the zeolite and a copper salt as described above under "solid state ion exchange" is made.
  • Said mixture is then heated to a temperature of 550 to 900°C, whereby the copper salt decomposes into the metal (i.e. copper) or the copper ion.
  • the mixture is heated at a temperature and for a time span sufficient to achieve the solid state sublimation of copper into the CHA framework type material.
  • the powder thus obtained is then dispersed in water and mixed with a binder.
  • Suitable binders are, for example, boehmite and silica gel.
  • this mixture comprising water, a binder, and the zeolite only needs to be stirred or homogenized, respectively, and may be applied directly as a coating suspension to coat a carrier substrate.
  • the coating suspension is hereinafter referred to as the "washcoat”.
  • said SCR catalyst is present in the form of a coating on a carrier substrate.
  • Carrier substrates can be so-called flow-through substrates or wall-flow filters, respectively.
  • Both carrier substrate may consist of inert materials, such as silicon carbide, aluminium titanate, cordierite or metal.
  • carrier substrates are well-known to the skilled person and available on the market.
  • the carrier substrates may be catalytically active on their own, and they may comprise catalytically active material, e.g. SCR-catalytically active material.
  • SCR-catalytically active materials which are suitable for this purpose are basically all materials known to the skilled person, for example catalytically active materials based on mixed oxides, or catalytically active materials based on ion-exchanged zeolitic compounds.
  • catalytically active materials based on mixed oxides or catalytically active materials based on ion-exchanged zeolitic compounds.
  • iron- and copper-exchanged zeolitic compounds are well known catalytically active materials.
  • mixed oxides comprising compounds of vanadium, titanium and tungsten are particularly suitable for this purpose.
  • these carrier substrates comprise a matrix component. All inert materials which are otherwise used for the manufacturing of catalyst substrates may be used as matrix components in this context. It deals, for instance, with silicates, oxides, nitrides or carbides, with magnesium aluminium silicates being particularly preferred.
  • the catalyst itself forms part of the carrier substrate, for example as part of a flow-through substrate or a wall-flow filter.
  • carrier substrates additionally comprise the matrix components described above.
  • Carrier substrates comprising the SCR catalysts according to the present invention may be used as such in exhaust purification. Alternatively, they may be coated with catalytically active materials, for example with SCR-catalytically active materials. Insofar as these materials shall exhibit an SCR catalytic activity, the SCR catalysts mentioned above are suitable materials.
  • catalytically active carrier materials are manufactured by mixing 10 to 95 wt.-% of an inert matrix component and 5 to 90 wt.-% of a catalytically active material, followed by extruding the mixture according to well-known protocols.
  • inert materials that are usually used for the manufacture of catalyst substrates may be used as the matrix components in this embodiment.
  • Suitable inert matrix materials are, for example, silicates, oxides, nitrides and carbides, with magnesium aluminium silicates being particularly preferred.
  • the application of the catalytically active catalyst onto either the inert carrier substrate or onto a carrier substrate which is catalytically active on its own as well as the application of a catalytically active coating onto a carrier substrate, said carrier substrate comprising a catalyst according to the present invention can be carried out following manufacturing processes well known to the person skilled in the art, for instance by widely used dip coating, pump coating and suction coating, followed by subsequent thermal post-treatment (calcination).
  • the average pore sizes and the mean particle size of the catalysts according to the present invention may be adjusted to one another in a manner that the coating thus obtained is located onto the porous walls which form the channels of the wall-flow filter (on-wall coating).
  • the average pore sizes and the mean particle sizes are preferably adjusted to one another in a manner that the catalyst according to the present invention is located within the porous walls which form the channels of the wall-flow filter.
  • the inner surfaces of the pores are coated (in-wall coating).
  • the mean particle size of the catalysts according to the present invention has to be sufficiently small to be able to penetrate the pores of the wall-flow filter.
  • the catalysts according to the present invention may advantageously be used for the exhaust purification of lean combustion engines, in particular for diesel engines. They convert nitrogen oxides comprised in the exhaust gas into the harmless compounds nitrogen and water.
  • DOC oxidation catalyst
  • SCR selective catalytic reduction type catalyst
  • DOC oxidation catalyst
  • DPF diesel particulate filter
  • combustible particle components are deposited on the DPF and combusted therein.
  • Such arrangements are, for instance, disclosed in EP 1 992 409 A1 .
  • Widely used arrangements of such catalysts are, for example (from upstream to downstream): (1) DOC + (NH 3 ) + SCR (2) DOC + DPF + (NH 3 ) + SCR (3) DOC + (NH 3 ) + SCR + DPF (4) DOC + (NH 3 ) + SCR + DOC + DPF.
  • (NH 3 ) represents a position where an urea aqueous solution, an aqueous ammonia solution, ammonium carbamate, ammonium formiate or the like is supplied as a reducing agent by spraying.
  • the supply of such urea or ammonia compounds in automotive exhaust gas purification systems is well known in the art.
  • the present invention furthermore refers to a method for the purification of exhaust gases of lean combustion engines, characterized in that the exhaust gas is passed over a catalyst according to the present invention.
  • ammonia is used as the reducing agent.
  • the ammonia required may, for instance, be formed within the exhaust purification system upstream to a particulate filter by means of an upstream nitrogen oxide storage catalyst ("lean NOx trap" - LNT). This method is known as "passive SCR”.
  • ammonia may be supplied in an appropriate form, for instance in the form of urea, ammonium carbamate or ammonium formiate, and added to the exhaust gas stream as needed.
  • a widespread method is to carry along an aqueous urea solution and to and to dose it into the catalyst according to the present invention via an upstream injector as required.
  • the present invention thus also refers to a system for the purification of exhaust gases emitted from lean combustion engines, characterized in that it comprises a catalyst according to the present invention, preferably in the form of a coating on a carrier substrate or as a component of a carrier substrate, and an injector for aqueous urea solutions, wherein the injector is located upstream of the catalyst of the present invention.
  • the SCR reaction with ammonia proceeds more rapidly if the nitrogen oxides are present in an 1:1 mixture of nitrogen monoxide and nitrogen dioxide, or if the ratios of both nitrogen oxides are close to 1:1.
  • this SAE paper suggests to increase the amount of nitrogen dioxide by means of an oxidation catalyst.
  • the exhaust gas purification process according to the present invention may not only be applied in the standard SCR reaction, i.e. in the absence of nitrogen dioxide, but also in the rapid SCR reaction, i.e. when part of the nitrogen monoxide has been oxidized to nitrogen dioxide, thus ideally providing a 1:1 mixture of nitrogen monoxide and nitrogen dioxide.
  • the present invention therefore also relates to a system for the purification of exhaust gases from lean combustion engines, characterized in that it comprises an oxidation catalyst, an injector for aqueous urea solutions and a catalyst according to the present invention, preferably in the form of a coating on a carrier substrate or as a component of a carrier substrate.
  • platinum supported on a carrier support material is used as an oxidation catalyst.
  • any carrier material for platinum which is known to the skilled person as suitable material may be used without departing from the scope of the claims.
  • Said materials show a BET surface area of 30 to 250 m 2 /g, preferably 100 to 200 m 2 /g (measured according to DIN 66132).
  • Preferred carrier substrate materials are alumina, silica, magnesium dioxide, titania, zirconia, ceria and mixtures and mixed oxides comprising at least two of these oxides.
  • Particularly preferred materials are alumina and alumina/silica mixed oxides. If alumina is used, it is preferably stabilized, for instance with lanthanum oxide.
  • the exhaust gas purification system is arranged in an order wherein, in flow direction of the exhaust gas purification system, an oxidation catalyst is arranged first, followed by an injector for an aqueous urea solution, and finally a catalyst according to the present invention.
  • Cu-Tetraethylenepentamine complex (Cu-TEPA): 37.9 g tetraethylenepentamine (0.2 mole) was added under stirring to a solution consisting of 50 g CuSO 4 *5H 2 O (0.2 mole) in 200 g of H 2 O (1 M solution) and left to stir for 2 h at room temperature.
  • the zeolite produced was determined to have the CHA framework type code according to X-ray diffraction (see figure 1 ) with a Si/AI ratio of 4.3 and a CuO content of 7.5 wt.%.
  • Figure 3 shows the morphology and crystal size of the product obtained.
  • the Cu-CHA obtained above was subjected to NH 4 + ion exchange: until the Cu content was 4.0 wt.-% in copper content, calculated as CuO, and the Na content was in the range of 0.1 to 0.4 wt.-%, calculated as pure metal, wherein both ranges were based on the total weight of the zeolite.
  • the catalyst formulation of the Cu-SCR catalyst according to the invention was based on a CHA-zeolite material with a CuO-loading of 4.0 wt.% from the synthesis, with an SAR of about 8.6.
  • the sodium content was 1500 ppm or 0.15 wt.-%, respectively, and the BET surface area of the zeolite material was ⁇ 680 m 2 /g.
  • the comparative example Cu-zeolite catalyst was based on a CHA-zeolite material with an SAR of 28 and a CuO-loading of 4.0 wt.%.
  • the sodium content was ⁇ 200 ppm or ⁇ 0.02 wt.-%, respectively, and the BET surface are of the zeolite material was ⁇ 720 m 2 /g.
  • the resulting Cu-zeolite materials were coated onto ceramic cordierite substrates with a cell density of 400 cpsi (cells per square inch) and a wall thickness of 6.5 mil.
  • a binder was used in an amount of 12 wt.%, resulting in an overall washcoat loading amount of 150 g/L coated catalyst volume.
  • Ageing conditions of choice were 16 hours at 750°C using a forced flow-through of hydrothermal atmosphere containing 10 vol.% of oxygen, 10 vol.% of water vapor balanced by nitrogen.
  • SCR activity testing of the drilled cores of 1 inch diameter and 3 inch length was carried out in a feed gas mixture containing 500 ppm nitrogen monoxide (NO), 750 ppm ammonia (NH 3 ), 5 vol.% water vapor (H 2 O), 10 vol.% oxygen (O 2 ), 10 vol.% carbon dioxide (CO 2 ) and nitrogen balance.
  • the space velocity was 60.000 h-1.
  • Reaction temperatures evaluated were in the range of 175 to 650°C. Tests were carried out in fresh state as well as in the above described aged state. NOx concentration and N 2 O concentrations were measured after observation of stable product composition downstream the catalyst samples. The product gas stream components were evaluated by a FTIR-spectrometer.

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Claims (12)

  1. Kristalline kupferhaltige kleinporige Alumosilikatzeolithe, die eine maximale Porengröße von acht tetraedrischen Atomen aufweisen, wobei der Zeolith CHA ist, einen Kupfergehalt von 2 bis 7 Gew.-% aufweist, berechnet als CuO und bezogen auf das Gesamtgewicht des Zeolithen, und einen Gehalt an Alkalimetallkationen in einer Gesamtmenge von 0,1 bis 0,4 Gew.-%, berechnet als reine Metalle und bezogen auf das Gesamtgewicht des Zeolithen, wobei die Alkalimetalle ausgewählt sind aus Natrium, Kalium und Mischungen von Natrium und Kalium, einem SAR von 7 bis 9 und einer BET-Oberfläche von 600 bis 750 m2/g.
  2. Kristalline kupferhaltige kleinporige Alumosilikatzeolithe nach Anspruch 1, wobei das Atomverhältnis von Kupfer zu Aluminium im Bereich zwischen 0,003 und 0,6 liegt.
  3. Kristalline kupferhaltige kleinporige Alumosilikatzeolithe nach Anspruch 1 oder 2, wobei die Kristallitgröße zwischen 10 und 5000 nm liegt.
  4. Verfahren zur Herstellung eines kristallinen kupferhaltigen kleinporigen Alumosilikatzeolithen, der eine maximale Porengröße von acht tetraedrischen Atomen aufweist, wobei der Zeolith CHA ist, einen Kupfergehalt von 2 bis 7 Gew.-% aufweist, berechnet als CuO und bezogen auf das Gesamtgewicht des Zeolithen, und einen Gehalt an Alkalimetallkationen in einer Gesamtmenge von 0,1 bis 0,4 Gew.-%, berechnet als reine Metalle und bezogen auf das Gesamtgewicht des Zeolithen, wobei die Alkalimetalle ausgewählt sind aus Natrium, Kalium und Mischungen von Natrium und Kalium, einem SAR von 7 bis 9 und einer BET-Oberfläche von 600 bis 750 m2/g, umfassend
    • Herstellen einer wässrigen Reaktionsmischung, umfassend einen Zeolithen vom Faujasit-Gerüsttyp, Cu-Tetraethylenpentamin (Cu-TEPA) und mindestens eine Verbindung M(OH)x, wobei M(OH)x NaOH und/oder KOH ist, und
    ∘ wobei Cu-TEPA in einer Menge von 0,0001 Mol/Gew. Cu-TEPA/FAU Zeolith bis 0,0016 Mol/Gew. Cu-TEPA/FAU Zeolith verwendet wird, und
    ∘ wobei M(OH)x in einer Menge von 0,001 Mol/Gew. M(OH)x/FAU-Zeolith bis 0,025 Mol/Gew. M(OH)x/FAU-Zeolith verwendet wird, und
    • Erwärmen der Reaktionsmischung für 2 bis 31 Tage bei Temperaturen von 80 bis 150 °C, um einen kupferhaltigen kleinporigen Zeolithen zu bilden,
    • Kalzinieren des kupferhaltigen kleinporigen Zeolithen für 1 bis 5 Stunden bei Temperaturen zwischen 500 °C und 650 °C, gefolgt von Einstellen des Kupfer- und Alkalimetallgehalts des Zeolithen durch lonenaustausch oder
    • Einstellen des Kupfer- und Alkalimetallgehalts des kupferhaltigen kleinporigen Zeolithen durch lonenaustausch, gefolgt von Kalzinieren des Zeolithen für 1 bis 5 Stunden bei Temperaturen zwischen 500 °C und 650 °C.
  5. Verfahren nach Anspruch 4, das umfasst
    • Herstellen einer wässrigen Reaktionsmischung, umfassend einen Zeolithen vom Faujasit-Gerüsttyp, Cu-Tetraethylenpentamin (Cu-TEPA) und mindestens eine Verbindung M(OH)x, wobei
    • M(OH)x NaOH und/oder KOH ist, und
    ∘ wobei Cu-TEPA in einer Menge von 0,0001 Mol/Gew. Cu-TEPA/FAU Zeolith bis 0,0016 Mol/Gew. Cu-TEPA/FAU Zeolith verwendet wird, und
    ∘ wobei M(OH)x in einer Menge von 0,001 Mol/Gew. M(OH)x/FAU-Zeolith bis 0,025 Mol/Gew. M(OH)x/FAU-Zeolith verwendet wird, und
    • wobei die wässrige Reaktionsmischung das Tetraethylammoniumkation nicht umfasst, und
    • Erwärmen der Reaktionsmischung für 2 bis 31 Tage bei Temperaturen von 80 bis 150 °C, um einen kupferhaltigen kleinporigen Zeolithen zu bilden,
    • Kalzinieren des kupferhaltigen kleinporigen Zeolithen für 1 bis 5 Stunden bei Temperaturen zwischen 500 °C und 650 °C, gefolgt von Einstellen des Kupfer- und Alkalimetallgehalts des Zeolithen durch lonenaustausch oder
    • Einstellen des Kupfer- und Alkalimetallgehalts des kupferhaltigen kleinporigen Zeolithen durch lonenaustausch, gefolgt von Kalzinieren des Zeolithen für 1 bis 5 Stunden bei Temperaturen zwischen 500 °C und 650 °C.
  6. Verfahren nach Anspruch 4 oder 5, wobei Tetraethylenpentamin das einzige Struktursteuerungsmittel in der Reaktionsmischung ist.
  7. Verfahren nach einem der Ansprüche 4 bis 6, wobei der Zeolith vom Faujasit-Gerüsttyp ein Si/Al-Verhältnis im Bereich von 5 bis 30 aufweist.
  8. Washcoat, umfassend einen kristallinen Alumosilikatzeolithen nach einem der Ansprüche 1 bis 3.
  9. Verwendung eines kristallinen Alumosilikatzeolithen nach einem der Ansprüche 1 bis 3 in der SCR-Katalyse.
  10. SCR-Katalysator, umfassend einen kristallinen Alumosilikatzeolithen nach einem der Ansprüche 1 bis 3.
  11. SCR-Katalysator, umfassend den Washcoat nach Anspruch 8.
  12. Abgasreinigungssystem, enthaltend einen SCR-Katalysator nach einem der Ansprüche 10 oder 11.
EP17166394.1A 2017-04-12 2017-04-12 Kupfer enthaltende, kleinporige zeolite mit niedrigerm alkalimetallgehalt, verfahren zu ihrer herstellung und ihre verwendung als scr-katalysatoren Active EP3388392B1 (de)

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EP17166394.1A EP3388392B1 (de) 2017-04-12 2017-04-12 Kupfer enthaltende, kleinporige zeolite mit niedrigerm alkalimetallgehalt, verfahren zu ihrer herstellung und ihre verwendung als scr-katalysatoren
EP18717894.2A EP3609838A1 (de) 2017-04-12 2018-04-10 Kupfer enthaltende kleinporige zeolithen mit niedrigem alkalimetallgehalt, verfahren zur herstellung davon und ihre verwendung als scr-katalysatoren
CN201880024780.XA CN110546108B (zh) 2017-04-12 2018-04-10 具有低碱金属含量的含铜小孔沸石、其制备方法以及它们作为scr催化剂的用途
PCT/EP2018/059156 WO2018189177A1 (en) 2017-04-12 2018-04-10 Copper-containing small-pore zeolites having a low alkali metal content, method of making thereof, and their use as scr catalysts

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EP18717894.2A Withdrawn EP3609838A1 (de) 2017-04-12 2018-04-10 Kupfer enthaltende kleinporige zeolithen mit niedrigem alkalimetallgehalt, verfahren zur herstellung davon und ihre verwendung als scr-katalysatoren

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JPWO2020085168A1 (ja) * 2018-10-23 2021-09-30 エヌ・イーケムキャット株式会社 Ｃｕ−Ｐ共担持ゼオライトの製造方法、これに用いることが可能な触媒前駆体組成物及び処理液、並びに積層触媒の製造方法
CN109364989B (zh) * 2018-11-20 2020-09-11 中国科学院生态环境研究中心 一种改性Cu-SSZ-13催化剂及其制备方法和用途
CN111871452A (zh) * 2020-08-10 2020-11-03 中触媒新材料股份有限公司 一种用于柴油车尾气净化cha型分子筛、催化剂及制备方法与应用
CN117120374A (zh) * 2021-04-09 2023-11-24 优美科股份公司及两合公司 过渡金属促进的菱沸石的一锅合成
CN114044524B (zh) * 2021-11-26 2023-07-04 中触媒新材料股份有限公司 一种复合模板剂制备的cha分子筛以及应用其制备scr催化剂的方法
WO2023180460A1 (en) 2022-03-23 2023-09-28 Umicore Ag & Co. Kg Copper and manganese containing chabazite scr catalyst for n2o reduction
WO2023180462A1 (en) 2022-03-23 2023-09-28 Umicore Ag & Co. Kg Scr zeolite catalysts for reduced n2o formation
WO2023180461A1 (en) 2022-03-23 2023-09-28 Umicore Ag & Co. Kg Scr zeolite catalysts for improved nox reduction
DE102022130469A1 (de) 2022-11-17 2024-05-23 Umicore Ag & Co. Kg Verfahren und Vorrichtung zum Herstellen eines Substrats für eine Abgasnachbehandlungseinrichtung

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